TW201902649A - Method for producing fiber reinforced plastic precursor and method for manufacturing fiber reinforced plastic - Google Patents

Abstract

Provided are: a method for manufacturing an FRP precursor in which workability is good, the discharge of resin from an end portion of an aggregate can be suppressed, and the method involves adhering a resin film to the aggregate under atmospheric pressure, wherein the resin-filling property of the aggregate with respect to bulk voids is excellent; and a method for manufacturing an FRP. Specifically, provided is a method for manufacturing an FRP precursor by adhering a thermosetting resin film onto one surface of a sheet-shaped aggregate under atmospheric pressure, the method comprising a step for heating and pressure-adhering the film and the aggregate by means of a press roll having a temperature in the range of +5 DEG C to +35 DEG C, said temperature being the temperature at which the minimum melt viscosity of the thermosetting resin film is exhibited.

Description

Manufacturing method of fiber-reinforced plastic precursor and manufacturing method of fiber-reinforced plastic

The invention relates to a method for manufacturing a fiber-reinforced plastic precursor and a method for manufacturing a fiber-reinforced plastic.

FRP (Fiber Reniforced Plastics) is a composite material that uses a material with a high modulus of elasticity such as fiber as the aggregate material, and places the aggregate material in a matrix material (matrix) such as plastic In order to improve the strength, it is a composite material that can exhibit weather resistance, heat resistance, chemical resistance, and light weight, and is inexpensive, lightweight, and highly durable. Taking advantage of these properties, fiber-reinforced plastics are used in a wide range of fields. For example, this fiber-reinforced plastic is used in structural materials such as residential equipment, ships, vehicles, and aircraft due to its styling and high strength. It also has insulation properties and is used in a wide range of fields such as electronic equipment. Examples of the fiber-reinforced plastic used in electronic equipment include prepregs. Fiber-reinforced plastics, such as prepregs before curing, are sometimes called fiber-reinforced plastic precursors.

As a method for manufacturing fiber-reinforced plastic, the following methods can be cited: (1) RTM (Resin Transfer Molding, resin transfer molding) method, which involves injecting resin into a mold in which the aggregate is tiled; (2) hand product (Hand Lay-up) method and spray up method, which are multi-layer lamination while laying down the aggregate and degassing the resin; and (3) SMC (Sheet Molding Compound) The compression method uses a mold to compression-mold a sheet-like material prepared by mixing a bone material and a resin in advance.

When using fiber-reinforced plastics for printed wiring boards, the thickness of fiber-reinforced plastics for printed wiring boards is required to be thinner than that of fiber-reinforced plastics for other uses. In addition, fiber-reinforced plastics for printed wiring boards are required to have the following high specifications: the tolerance range of the thickness variation of the fiber-reinforced plastics after molding is small, and there is no void or the like. Therefore, most fiber-reinforced plastics for printed circuit boards are manufactured by the Hand Lay-up (HLU) method. The hand product method is a manufacturing method in which a varnish obtained by dissolving a resin is applied to a bone material using a coater, followed by drying, solvent removal, and thermal curing (see Patent Document 1). In this hand accumulation method, if a thermosetting resin is applied to the aggregate in advance, workability can be improved, and the load on the surrounding environment can be reduced.

However, when uncured polyaramide nonwoven fabric, thin fiberglass paper, or thin woven fabric is used as the aggregate material, these materials have low strength when used as the aggregate material. Therefore, workability in the following cases Poor: When the varnish is applied and the solvent is removed, dried, and heat hardened, the weight of the varnish will exceed the weight of the aggregate and cause the aggregate to break; or, when the coating machine is reduced in order to adjust the amount of resin to be applied When the gap (gap), it will tear the bone and so on.

In addition, fiber-reinforced plastics for printed wiring boards need to take into account both the high precision of the thickness after lamination and the filling (moldability) of the resin with the inner circuit pattern. Therefore, it is necessary to use one kind of bone material to manufacture a plurality of fiber-reinforced plastic precursors, so the manufacturing conditions are complicated. The plurality of fiber-reinforced plastic precursors are fiber-reinforced plastic precursors that have a mass difference of several percent by mass of resin attached to the bone material , Fiber-reinforced plastic precursors made by changing the curing time of thermosetting resins, and fiber-reinforced plastic precursors made by combining them. Furthermore, in order to manufacture by changing various coating conditions, the loss of materials used in manufacturing is also large.

Therefore, a method for manufacturing a fiber-reinforced plastic precursor has been proposed, which does not directly coat the thermosetting resin on the bone material, but has the following steps: a film obtained by making the thermosetting resin into a thin film is prepared in advance A resin film is used, and the aggregate is bonded to the resin film under reduced pressure, and then heat-treated (see Patent Document 2). [Prior Art Literature] (Patent Literature)

Patent Document 1: Japanese Patent Application Laid-Open No. 01-272416 Patent Document 2: Japanese Patent Application Laid-Open No. 2011-132535

[Problems to be Solved by the Invention] However, in the method described in Patent Document 2, if the bonding of the aggregate and the resin film is performed under a reduced pressure, it is difficult to cope with the failure, and it is necessary to cope with the resin from the end of the aggregate. In the case of partial extrusion, the efficiency such as workability under the reduced pressure condition is inherently poor. Therefore, in order to avoid the above-mentioned problems, a method of bonding the aggregate material to the resin film under atmospheric pressure has been considered. However, according to the research of the present inventors, when only the atmospheric pressure is applied, the resin has a poor filling property for the aggregate material. Pores are created. Therefore, the problem to be solved by the present invention is to provide a method for manufacturing a fiber-reinforced plastic precursor and a method for manufacturing the fiber-reinforced plastic. The method for manufacturing the fiber-reinforced plastic precursor has good workability and can suppress the resin from the end of the aggregate When the resin film is adhered to the aggregate under atmospheric pressure in the case of extrusion, the resin has excellent resin filling properties for the volume voids of the aggregate. [Technical means to solve the problem]

As a result of intensive research in order to solve the above-mentioned problems, the inventors have found that after the resin film is adhered to the aggregate under atmospheric pressure, the above-mentioned problems can be solved by pressing them with a roller under specific conditions, thereby completing the present invention. The present invention has been completed based on such knowledge and insights.

The present invention relates to the following techniques [1] to [7]. [1] A method for manufacturing a fiber-reinforced plastic precursor, wherein a fiber-reinforced plastic precursor is manufactured by adhering a thermosetting resin film on one surface of a sheet-like bone material under atmospheric pressure, wherein the manufacturing method includes The following steps: The film and the aggregate are heated and pressure-bonded by a pressure roller having a temperature within a range of + 5 ° C to + 35 ° C, which is the temperature at which the thermosetting resin film exhibits the lowest melt viscosity. [2] The method for producing a fiber-reinforced plastic precursor according to the above [1], wherein a roller linear pressure of the pressure roller is 0.2 to 1.0 MPa. [3] The method for producing a fiber-reinforced plastic precursor according to the above [1] or [2], wherein a roller line pressure of the pressure roller is 0.4 to 1.0 MPa. [4] A method for manufacturing a fiber-reinforced plastic, comprising the steps of using a fiber-reinforced plastic precursor obtained by the method for manufacturing a fiber-reinforced plastic precursor described in any one of [1] to [3] above.物 curing. [5] A method for manufacturing a fiber-reinforced plastic precursor, wherein a fiber-reinforced plastic precursor is manufactured by adhering a thermosetting resin film on one surface of a sheet-like bone material under atmospheric pressure, wherein the manufacturing method includes The following steps: (1) The film and the aggregate are heated and pressure-bonded by a pressure roller and a roll line pressure of 0.4 to 1.0 MPa. [6] The method for producing a fiber-reinforced plastic precursor as described in [5], wherein the temperature of the pressure roller is lower than the temperature at which the thermosetting resin film exhibits the lowest melt viscosity + 5 ° C. [7] A method for manufacturing a fiber-reinforced plastic, comprising the steps of hardening a fiber-reinforced plastic precursor obtained by the method for manufacturing a fiber-reinforced plastic precursor described in [5] or [6] above. [Effect of the invention]

According to the present invention, it is possible to provide a method for producing a fiber-reinforced plastic precursor and a method for producing a fiber-reinforced plastic. The method for producing a fiber-reinforced plastic precursor has good workability and can suppress the resin from extruding from the end of the aggregate. In addition, in a method of attaching a resin film to an aggregate under atmospheric pressure, the resin has excellent filling properties for the volume voids of the aggregate.

[Method for Producing Fiber-Reinforced Plastic Precursor] One aspect of the present invention is a method for producing a fiber-reinforced plastic precursor, in which a thermosetting resin film (hereinafter, sometimes referred to as a resin film) is produced at atmospheric pressure. A fiber-reinforced plastic precursor is manufactured by sticking to one surface of the sheet-shaped aggregate, wherein the manufacturing method includes the following steps: heating and crimping the film and the aggregate with a pressure roller, and the pressure The roll has a temperature in a range of + 5 ° C to + 35 ° C, which is the temperature at which the thermosetting resin film exhibits the lowest melt viscosity. Furthermore, another aspect of the present invention is a method for manufacturing a fiber-reinforced plastic precursor, which manufactures a fiber-reinforced plastic precursor by attaching a thermosetting resin film to one surface of a sheet-like bone material under atmospheric pressure. Wherein, the manufacturing method includes the following steps: the pressing of the film and the aggregate by pressing the roller with a roll line pressure of 0.4 to 1.0 MPa, and performing pressure bonding.

Hereinafter, with reference to FIG. 1, the embodiment of the manufacturing method of the fiber-reinforced plastic precursor and the manufacturing apparatus 1 of the fiber-reinforced plastic precursor which can be used for this manufacturing method are demonstrated. The device 1 for manufacturing a fiber-reinforced plastic precursor is described as a device capable of adhering a pair of resin films (thermosetting resin films) 54 to both sides of a sheet-like bone material 40. However, it is also possible to adopt a device capable of adhering only one resin film 54 to one surface of the sheet-like bone material 40. At this time, in the first figure, one of the following devices located below (or above) the aggregate 40 is not needed: the resin film feeding device 3, the protective film peeling mechanism 4, and the protective film winding device 5 . The device 1 for manufacturing a fiber-reinforced plastic precursor is placed under atmospheric pressure. The manufacturing method of the fiber-reinforced plastic precursor in this invention can be implemented using the fiber-reinforced plastic precursor manufacturing apparatus 1. Here, in this specification, "under atmospheric pressure" is synonymous with "under normal pressure." When the fiber-reinforced plastic precursor is produced under atmospheric pressure, it is possible to avoid workability problems that easily occur when, for example, a vacuum laminator is used.

An apparatus 1 for manufacturing a fiber-reinforced plastic precursor includes: an aggregate delivery device 2, a pair of resin film delivery devices 3 and 3, a sheet heating and compression bonding device 6, and a fiber-reinforced plastic precursor winding device 8. The apparatus 1 for manufacturing a fiber-reinforced plastic precursor preferably further includes a sheet pressure cooling device 7, a pair of protective film peeling mechanisms 4 and 4, and a pair of protective film winding devices 5 and 5.

The aggregate sending device 2 is a device that rotates the roll wound with the sheet-like aggregate 40 in a direction opposite to the winding direction, and sends out the aggregate 40 wound on the roll. In FIG. 1, the aggregate feeding device 2 sends the aggregate 40 from the lower side of the roller toward the sheet heating and compression bonding device 6.

A pair of resin film feeding devices 3 and 3 are provided with a roller around which the resin film 50 with a protective film is wound, and a support mechanism that applies a specific tension to the resin film 50 with the protective film that is sent out One side supports the roller in a rotatable manner; and the device rotates the roller wound with the protective film-attached resin film 50 in the direction opposite to the winding direction to protect the wound roller. The thin resin film 50 is sent out. The protective film-attached resin film 50 is a thin film including: a resin film 54; and a protective film 52 which is laminated on one of the resin-side film-side film surfaces (two of the resin film 54) Of the surfaces, the surface on the side of the aggregate 40) 54a.

A pair of resin film feeding devices 3 and 3 are each located on the front surface 40a side and the back surface 40b side of the bone material 40 to be fed. Among them, a resin film sending device 3 is located on the surface 40a side of the delivered bone material 40, and the sending device attaches a protective film in such a manner that the protective film 52 will become the side of the delivered bone material 40. The resin film 50 is fed from the lower side of the roller toward one of the protective film peeling mechanisms 4. Similarly, another resin film sending device 3 is located on the back surface 40b side of the sent-out bone material 40, and the sending-out device attaches the other so that the protective film 52 will be the side of the sent-out bone material 40. The resin film 50 of the protective film is sent from the upper side of the roller toward the other protective film peeling mechanism 4.

The pair of protective film peeling mechanisms 4 and 4 are rotating rollers respectively located on the front surface 40a side and the back surface 40b side of the fed-out bone material 40. One of the protective film peeling mechanisms 4 is a mechanism for peeling one of the protective films 52 from one of the resin films 50 with the protective film attached to it. The peeling mechanism is to remove the following methods: The resin film 50 of the protective film abuts against the surface of the rotating roller that is rotating, and then one of the resin films 54 of the resin film 50 with the protective film attached is advanced toward the sheet heating and crimping device 6 and one of the protective films is advanced. 52 is advanced toward one of the protective film winding devices 5, and the resin film 50 with the protective film is fed from one of the resin film feeding devices 3, and is advanced toward one of the protective film peeling mechanisms 4. As a result, the bone-side film surface 54a of one of the resin films 54 is exposed. Similarly, another protective film peeling mechanism 4 is a mechanism for peeling another protective film 52 from another resin film 50 with a protective film attached, and the peeling mechanism is used to peel off in the following manner: Hold the other protective film-attached resin film 50 against the surface of the rotating roller, and then advance the other resin film 54 of the other protective film-attached resin film 50 toward the sheet heating and crimping device 6, and The other protective film 52 is advanced toward the other protective film winding device 5, and the other protective film-attached resin film 50 is fed from the other resin film feeding device 3, and faces the other protective film peeling mechanism 4. go ahead. Thereby, the aggregate-side film surface 54 a of the other resin film 54 is exposed.

A pair of protective film winding devices 5 and 5 are respectively located on the front surface 40a side and the back surface 40b side of the delivered aggregate 40, and are used to wind up the protection after the pair of protective film peeling mechanisms 4 and 4 are peeled off. Films 52 and 52 take-up device.

The sheet heating and pressure bonding apparatus 6 includes a pair of pressure rollers and a mechanism (not shown) for applying a compressive force to the pair of pressure rollers. The pair of pressure rollers has a heating body inside, and can be heated at a specific set temperature.

The sheet heating and crimping device 6 uses a pair of rotating pressure rollers to crimp the resin films 54 and 54 onto the fed bone material 40 to form a sheet-like fiber-reinforced plastic precursor 60 (film crimping). Step), and the fiber-reinforced plastic precursor 60 is sent toward the sheet pressure cooling device 7. Specifically, each of the resin films 54 and 54 sent from the pair of protective film peeling devices 4 and 4 is laminated on the front surface 40 a and the back surface 40 b of the bone material 40 sent from the bone material feeding device 2. The aggregate 40 sent from the aggregate sending device 2 and the resin films 54 and 54 sent from the pair of protective film peeling devices 4 and 4 are fed between a pair of pressure rollers. At this time, one of the resin films 54 is laminated on the bone material 40 such that the bone material side film surface 54 a side of the one resin film 54 is adhered to the surface 40 a side of the bone material 40, and the other resin film 54 is In the manner that the surface 54a side of the aggregate material side film is adhered to the back surface 40b side of the aggregate material 40, another resin film 54 is laminated on the aggregate material 40 to form a fiber-reinforced plastic precursor 60. The fiber-reinforced plastic precursor 60 sent from the sheet heating and crimping device 6 is in a high temperature state.

The sheet pressure cooling device 7 includes a pair of cooling pressure rollers and a mechanism (not shown) for applying a compressive force to the pair of cooling pressure rollers. A pair of cooling and pressurizing rollers, using a pair of rotating cooling and pressurizing rollers, can compress and cool the high-temperature fiber-reinforced plastic precursor 60 sent from the sheet heating and crimping device 6, and then send it to the fiber-reinforced plastic precursor. Take-up device 8.

The fiber-reinforced plastic precursor take-up device 8 includes a take-up roller that takes up a sheet-shaped fiber-reinforced plastic precursor 60 sent from the sheet pressure cooling device 7; and a drive mechanism (not shown), It rotates the roller.

The above-mentioned manufacturing apparatus 1 for a fiber-reinforced plastic precursor is operated in the following manner.

First, the sheet-shaped bone material 40 is sent out from the bone material feeding device 2 toward the sheet heating and pressure bonding device 6. At this time, the front surface 40a and the back surface 40b of the aggregate 40 are exposed.

In addition, the protective film 52 peels one of the resin films 50 with a protective film in such a manner that it becomes the side of the bone material 40 to be fed, and peels the lower side of the roller of one of the resin film feeding devices 3 toward one of the protective films Divide mechanism 4 to send. In addition, the protective film 52 peels off the other resin film 50 with the protective film from the upper side of the roller of the other resin film feeding device 3 so as to be the side of the bone material 40 to be sent out toward the other protective film. Agency 4 sends out.

Then, one of the sent out resin films 50 with a protective film is hung on one of the protective film peeling mechanisms 4, that is, a rotating roller, and is rotated to expose the surface 54a of the aggregate-side film by one of them. The protective film-attached resin film 50 peels off one of the protective films 52, and advances one of the resin films 54 toward the sheet heating and compression bonding device 6. As a result, the bone-side film surface 54a of one of the resin films 54 is exposed. Similarly, when another sent-out resin film 50 with a protective film is hung on another protective film peeling mechanism 4 that is a rotating roller to rotate, the film surface 54a of the aggregate-side film is exposed by another A protective film-attached resin film 50 peels off the other protective film 52 and advances the other resin film 54 toward the sheet heating and compression bonding device 6. Thereby, the bone-side film surface 54a of the other resin film 54 is exposed. The peeled pair of protective films 52 and 52 are wound up by a pair of protective film winding devices 5 and 5, respectively.

The resin film 54 and 54 are laminated on the bone material 40 sent from the bone material sending device 2, and the bone material 40 sent from the bone material sending device 2 and the pair of protective film peeling mechanisms 4 are laminated. The resin films 54 and 54 sent out by and 4 are fed between a pair of pressure rollers. Further, a pair of resin films 54 and 54 are pressure-bonded to the bone material 40 using a sheet heating and pressure-bonding device 6 under normal pressure to obtain a fiber-reinforced plastic precursor 60 (film pressure-bonding step). At this time, by controlling the temperature of the heating body, a pair of pressure rollers can be maintained at a constant temperature, and the film can be pressurized while being heated during the film crimping step. The heating body is provided in the sheet heating and crimping device 6. Of a pair of pressure rollers.

Here, in one aspect of the present invention, when the resin film is heated and pressed on the aggregate, from the viewpoint of the resin filling property, the temperature of the pressure roller is preferably the lowest melting temperature of the resin film. The viscosity temperature is a temperature in the range of + 5 ° C to + 35 ° C, more preferably the temperature at which the resin film exhibits the lowest melt viscosity + 8 ° C to + 32 ° C, and further preferably the temperature at which the resin film exhibits the lowest melt viscosity + 10 ° C to + 30 ° C. The temperature at which the resin film exhibits the lowest melt viscosity is a value measured using a rheometer, and more specifically, a value measured according to the method described in the examples. When the temperature of the pressure roller is this condition, from the viewpoint of the resin filling property, the roll line pressure of the pressure roller is preferably 0.2 to 1.0 MPa, more preferably 0.4 to 1.0 MPa, and still more preferably 0.4 to 0.6. MPa.

Furthermore, in another aspect of the present invention, when the resin film is heated and pressed on the aggregate, even if the temperature of the pressure roller is lower than the temperature at which the resin film shows the lowest melt viscosity + 5 ° C, as long as the roller of the pressure roller When the linear pressure is 0.4 to 1.0 MPa, sufficient resin filling properties can be obtained. The roll line pressure at this time may be 0.4 to 0.8 MPa, may be 0.4 to 0.7 MPa, or may be 0.4 to 0.6 MPa.

In the present invention, the temperature at which the resin film exhibits the lowest melt viscosity varies depending on the material of the resin film. From the viewpoint of the productivity of the fiber-reinforced plastic precursor, it is preferably 60 to 150 ° C, and more preferably 80 to 140. The temperature is more preferably 100 to 140 ° C, and particularly preferably 120 to 140 ° C.

The fiber-reinforced plastic precursor 60 sent out from the sheet heating and crimping device 6 is further pressurized and cooled by the sheet pressure-cooling device 7. The fiber-reinforced plastic precursor winding device 8 is used to wind up the fiber-reinforced plastic precursor 60 sent from the sheet pressure cooling device 7.

[Manufacturing method of fiber-reinforced plastic] The present invention also provides a method for manufacturing fiber-reinforced plastic, which has the following steps: hardening the fiber-reinforced plastic precursor obtained by the aforementioned method for manufacturing a fiber-reinforced plastic precursor (C stage)化). The conditions for hardening the fiber-reinforced plastic precursor are not particularly limited, but it is preferably hardened by heating at 160 to 250 ° C. for 15 to 60 minutes. Furthermore, when manufacturing fiber-reinforced plastics for printed wiring boards, a laminated body containing fiber-reinforced plastics can be formed by: one sheet of fiber-reinforced plastic precursor or two to twenty fiber-reinforced plastic precursors A metal foil is placed on the superimposed object, and it is laminated and formed under the conditions of a temperature of 100 to 250 ° C., a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours. In this way, it is not necessary to harden the fiber-reinforced plastic precursor alone, and it is also possible to harden the fiber-reinforced plastic precursor in a state of being laminated with metal foil or various resin films.

Hereinafter, the bone material and the resin film used in manufacturing the fiber-reinforced plastic precursor will be specifically described. [Aggregate] As the aggregate, various conventional aggregates used for laminated boards for electrical insulating materials can be used. Examples of the material of the aggregate include natural fibers such as paper and cotton wool; inorganic fibers such as glass fiber and asbestos; organic compounds such as polyaramide, polyimide, polyvinyl alcohol, polyester, tetrafluoroethylene, and acrylic acid Fiber; a mixture of these materials. Among them, glass fibers are preferred from the viewpoint of flame retardancy. Examples of glass fiber substrates include: woven fabrics made of E glass, C glass, D glass, S glass, etc., or glass woven fabrics made of organic fibers with short fibers adhered; glass fibers and cellulose Fiber blends, etc. More preferred is a glass woven fabric made of E glass. These aggregates have the following shapes: woven fabric, non-woven fabric, roving, chopped strand mat, surfacing mat, and the like. The material and shape are selected according to the intended use or performance of the molded product, and may be used alone, or two or more materials and shapes may be combined as needed.

[Resin film] The resin film used in the production method of the present invention is a thermosetting resin film, and is a resin film obtained by forming a thermosetting resin composition into a film shape. The thermosetting resin composition contains at least a thermosetting resin. In addition to the thermosetting resin, if necessary, examples include hardeners, hardening accelerators, inorganic fillers, organic fillers, coupling agents, leveling agents, antioxidants, flame retardants, flame retardant additives, and Denaturation imparting agent, thickener, thixotropy imparting agent, flexible material, surfactant, photopolymerization initiator and the like; it is preferable to contain at least one selected from these. Hereinafter, each component contained in a thermosetting resin composition is demonstrated in order.

(Thermosetting resin) Examples of the thermosetting resin include epoxy resin, phenol resin, unsaturated fluorene imine resin, cyanate resin, isocyanate resin, benzoxazine resin, and oxetane. Resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, triazine resin, melamine resin, urea resin, furan resin, etc. Moreover, it is not specifically limited to these thermosetting resins, A well-known thermosetting resin can be used. These thermosetting resins may be used individually by 1 type, and may use 2 or more types together. Among these, epoxy resin is preferred from the viewpoints of workability, moldability, and manufacturing cost.

Examples of the epoxy resin include a cresol novolac epoxy resin, a phenol novolac epoxy resin, a naphthol novolac epoxy resin, an aralkyl novolac epoxy resin, and a biphenol novolac epoxy resin. Novolac epoxy resin such as epoxy resin; bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, bisphenol S epoxy resin, bisphenol T epoxy resin Bisphenol epoxy resins such as bisphenol Z epoxy resin, tetrabromobisphenol A epoxy resin; biphenyl epoxy resin, tetramethylbiphenyl epoxy resin, bitriphenyl epoxy resin Biphenyl tetraphenyl epoxy resin, naphthol aralkyl epoxy resin, naphthol aralkyl epoxy resin, naphthol aralkyl epoxy resin, fluorene epoxy resin, dicyclopentadiene Epoxy skeleton epoxy resins, epoxy resins having an ethylenically unsaturated group in the skeleton, alicyclic epoxy resins; diglycidyl etherification of polyfunctional phenols; hydrogenated compounds of these epoxy resins, and the like. An epoxy resin may be used individually by 1 type, and may use 2 or more types together from a viewpoint of insulation reliability and heat resistance. Examples of commercially available epoxy resins include cresol novolac epoxy resin, which is "EPICLON (registered trademark) N-660" (manufactured by DIC Corporation), and bisphenol A epoxy resin, which is " EPICLON (registered trademark) 840S "(manufactured by DIC Corporation)," jER828EL "," YL980 "(the above are manufactured by Mitsubishi Chemical Corporation), etc.

Here, the epoxy resin is not particularly limited, and from the viewpoint of imparting flexibility, it may have two or more epoxy groups in one molecule, and the number of carbons derived from an alkylene group in the main chain may be 3 The epoxy resin of the structural unit of the above alkanediol. In addition, from the viewpoint of further improving the flexibility, the structural unit derived from an alkanediol having 3 or more carbons having an alkylene group can be continuously repeated 2 or more. The alkanediol having 3 or more carbon atoms is preferably an alkanediol having 4 or more carbon atoms. The upper limit of the carbon number of the alkylene group is not particularly limited, but is preferably 15 or more, more preferably 10 or less, and even more preferably 8 or less. As the epoxy resin, a halogenated epoxy resin can be used from the viewpoint of flame retardancy.

(Hardener) When the thermosetting resin is an epoxy resin as the hardener, phenol-based hardener, cyanate-based hardener, acid anhydride-based hardener, amine-based hardener, and compound containing an active ester group can be mentioned. And other hardeners for epoxy resins. When the thermosetting resin is a resin other than an epoxy resin, a known curing agent can be used as the curing agent for the thermosetting resin. A hardening agent may be used individually by 1 type, and may use 2 or more types together.

The phenol-based hardener is not particularly limited, and preferred examples include a cresol novolac-based hardener, a biphenyl-based hardener, a phenol novolac-based hardener, a naphthalene ether-based hardener, and a triazine skeleton-containing hardener. Phenol-based hardeners, etc. Examples of commercially available phenolic hardeners include cresol novolac-type hardeners such as KA-1160, KA-1163, and KA-1165 (all manufactured by DIC Corporation); MEH-7700, MEH-7810, MEH-7851 (both manufactured by Meiwa Chemical Co., Ltd.) and other biphenyl type hardeners; PHENOLITE (registered trademark) TD2090 (manufactured by DIC Corporation) and other phenol novolac type hardeners; EXB-6000 (manufactured by DIC Corporation) ) And other naphthalene ether-type hardeners; LA3018, LA7052, LA7054, LA1356 (all manufactured by DIC Corporation) and other phenol-based hardeners containing a triazine skeleton. Among them, a cresol novolac type hardener is preferred.

The cyanate-based curing agent is not particularly limited, and examples thereof include bisphenol A dicyanate and polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate). )), 4,4'-methylenebis (2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyldicyanate, hexafluorobisphenol A dicyanide Acid ester, 2,2-bis (4-cyano) phenylpropane, 1,1-bis (4-cyanophenylmethane), bis (4-cyano-3,5-dimethyl) Phenyl) methane, 1,3-bis (4-cyanophenyl-1- (methylethylene)) benzene, bis (4-cyanophenyl) sulfide, bis (4-cyanate Phenyl) ether and the like. The acid anhydride-based hardener is not particularly limited, and examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexadecane Hydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic acid, dodecenyl succinic anhydride, 5- (2,5-dimeric Oxytetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. The amine-based hardener is not particularly limited, and examples thereof include aliphatic amines such as triethylenetetramine, tetraethylenepentamine, and diethylaminopropylamine; m-phenylenediamine, and 4,4'-diamine Aromatic amines such as diphenylmethane. Moreover, as a hardening | curing agent, urea resin etc. can also be used.

When the thermosetting resin composition contains a curing agent, the content is preferably 20 to 150 parts by mass, more preferably 20 to 120 parts by mass, and still more preferably 40 to 100 parts by mass relative to 100 parts by mass of the thermosetting resin. Serving. The blending amount of the curing agent for epoxy resin is preferably an amount of 0.3 to 1.5 equivalents of the reactive group equivalent ratio of the curing agent to 1 epoxy equivalent of the epoxy resin. When the compounding quantity of an epoxy resin hardening | curing agent exists in the said range, it will be easy to control hardening degree, and productivity will become favorable.

(Hardening accelerator) As a hardening accelerator, the general hardening accelerator used at the time of hardening of the said thermosetting resin can be used. For example, when the thermosetting resin is an epoxy resin, examples of the curing accelerator include imidazole compounds and derivatives thereof; phosphorus-based compounds; tertiary amine compounds; and quaternary ammonium compounds. Among these, from the viewpoint of promoting the hardening reaction, imidazole compounds and derivatives thereof are preferred. Specific examples of the imidazole compound and its derivative include 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1, 2-dimethylimidazole, 2-ethyl-1-methylimidazole, 1,2-diethylimidazole, 1-ethyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 4 -Ethyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl 2-methylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole [1,2-a ] Benzimidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- [2' -Undecylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1') ] Imidazole compounds such as ethyl-s-triazine; modified imidazole compounds such as isocyanate-masked imidazole, epoxy-masked imidazole; trimellitic acid 1-cyanide Ethyl-2-phenyl imidazolium trimellitate and the imidazole compound of the tricarboxylic acid; isopropyl imidazole salt of the compound with the cyanuric acid; salts of the imidazole compound with hydrobromic acid. Among these, a modified imidazole compound is preferred, and an isocyanate-masked imidazole is more preferred. The imidazole compound may be used alone or in combination of two or more.

When the thermosetting resin composition contains a hardening accelerator, from the viewpoint of storage stability and physical properties of the thermosetting resin composition, the content is preferably 0.1 to 20 parts per 100 parts by mass of the thermosetting resin. It is more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 to 6 parts by mass.

(Inorganic Filler) The inorganic filler can improve the impermeability and abrasion resistance and reduce the thermal expansion rate. Examples of the inorganic filler include oxides such as silicon dioxide, aluminum oxide, zirconium dioxide, mullite, and magnesium oxide; hydroxides such as aluminum hydroxide, magnesium hydroxide, and hydrotalcite; nitriding Nitriding ceramics such as aluminum, silicon nitride and boron nitride; natural minerals such as talc, kaolinite, saponite; metal particles, carbon particles, etc. Among these, oxides and hydroxides are preferred, silicon dioxide and aluminum hydroxide are more preferred, and aluminum hydroxide is more preferred.

When the thermosetting resin composition contains an inorganic filler, the content also varies depending on the purpose of addition. The solid content of the thermosetting resin composition is preferably 0.1 to 65% by volume. For the purpose of coloring and impermeability, if it is 0.1% by volume or more, there is a tendency that a sufficient effect can be exhibited. On the other hand, when it is added for the purpose of increase, by controlling it to 65% by volume or less, the adhesive force tends to be suppressed, and the viscosity when the resin component is blended does not become too high, which makes it easy to suppress workability. Declining tendency. From the same viewpoint, it is more preferably 5 to 50% by volume, and still more preferably 10 to 40% by volume. Here, the solid content in the present specification refers to a component in a composition other than volatile materials such as moisture and an organic solvent described later. That is, the solid content includes components that are liquid, syrupy, and waxy at room temperature around 25 ° C, and do not necessarily mean solid.

(Coupling agent) By containing a coupling agent, it has the effect of improving the dispersibility of an inorganic filler and an organic filler, and the effect of improving the adhesiveness with respect to a base material. A coupling agent may be used individually by 1 type, and may use 2 or more types together. The coupling agent is preferably a silane-based coupling agent. Examples of the silane-based coupling agent include amine-based silane coupling agents [for example, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane Etc.], epoxysilane-based coupling agent [such as 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc.], phenyl Silane-based coupling agents, alkylsilane-based coupling agents, alkenylsilane-based coupling agents [eg, vinyltrichlorosilane, vinyltriethoxysilane and other vinylsilane-based coupling agents], alkynylsilane-based coupling agents, Halosilane-based coupling agents, silicone-based coupling agents, hydrogen-silane-based coupling agents, silazane-based coupling agents, alkoxysilane-based coupling agents, chlorosilane-based coupling agents, (meth) acrylic fluorenylsilane Coupling Agents, Amino Silane Coupling Agents, Isocyanuric Silane Coupling Agents, Urea Silane Coupling Agents, Mercapto Silane Coupling Agents, Sulfide Silane Coupling Agents, and Isocyano Silane Coupling agent, etc. Among them, an epoxysilane-based coupling agent is preferred, and 3-glycidoxypropyltrimethoxysilane is more preferred. A so-called titanate-based coupling agent may also be used, which is obtained by replacing a silane site with a titanate.

When the thermosetting resin composition contains a coupling agent, the content is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 4 parts by mass, and still more preferably 0.5 to 3 parts by mass relative to 100 parts by mass of the thermosetting resin. Serving. If it is 0.01 parts by mass or more, there is a tendency that the surface of the aggregate material and the surface of the filler can be sufficiently covered; if it is 5 parts by mass or less, there is a tendency that the generation of the remaining coupling agent can be suppressed.

(Organic solvent) From the viewpoint of making the operation easier, the resin composition may further contain an organic solvent. In this specification, a resin composition containing an organic solvent may be referred to as a resin varnish. When forming a resin film, it is preferable to use it as a resin varnish from a viewpoint of workability | operativity. The organic solvent is not particularly limited, and examples thereof include methanol, ethanol, propanol, butanol, methyl cyperidine, butyl cyperidine, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, and Alcohol solvents such as propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and tripropylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, 4-methyl Ketone solvents such as 2-pentanone; ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate; ether solvents such as tetrahydrofuran; aromatics such as toluene, xylene, and mesitylene Family solvents; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and other nitrogen atom-containing solvents; dimethylsulfine and other sulfur atom-containing solvents Solvents, etc. Among these, from the viewpoints of solubility and appearance after coating, a ketone solvent is preferred, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone is more preferred, and cyclohexanone is even more preferred. , Methyl ethyl ketone. An organic solvent may be used individually by 1 type, and may use 2 or more types together.

From the viewpoint of ease of coating, the content of the organic solvent is preferably adjusted such that the solid content of the resin composition becomes 20 to 85% by mass, and more preferably the resin composition is used. The amount of the organic solvent used was adjusted so that the solid content of the organic solvent became 40 to 80% by mass.

[Manufacturing method of thermosetting resin film] First, a resin varnish is prepared by adding the thermosetting resin to the organic solvent, adding other components as necessary, and then using various mixers Mix and stir. Examples of the mixer include a mixer of the following types: an ultrasonic dispersion method, a high-pressure collision dispersion method, a high-speed rotation dispersion method, a bead mill method, a high-speed shear dispersion method, and a revolution-revolution dispersion method. The obtained resin varnish is applied to a carrier film, and an unnecessary organic solvent is removed, and then semi-cured (B-staged), whereby a thermosetting resin film (resin film) can be produced. Examples of the carrier film include organic films such as polyethylene terephthalate (PET), biaxially stretched polypropylene (OPP), polyethylene, polyvinyl fluoride, and polyimide; copper, aluminum, and these Metal alloy thin films; films obtained by subjecting the surface of these organic thin films or metal thin films to release treatment with a release agent. Furthermore, when the manufactured resin film is wound up by a roller, if a surface is coated with a thermosetting resin composition and semi-hardened, a carrier film is disposed, and the thermosetting resin composition is sandwiched therebetween. When winding is carried out in a state, workability is good and good.

In addition, the thickness of the resin film is not particularly limited. When a resin film thinner than the thickness of the aggregate is used, two or more resin films can be adhered to one side of the aggregate. In addition, when two or more resin films are used, different resin films, such as the degree of thermal curing of the resin film or the blending composition, can be used in combination. Fiber-reinforced plastic precursors can be cut into any size according to needs, and adhered to specific objects according to needs, and then heat hardened. In addition, the fiber-reinforced plastic precursor can also be taken up on a roller in advance and used by a roll-to-roll process. [Example]

Next, the present invention will be described in more detail by the following examples, but the present invention is not limited to these examples. The fiber-reinforced plastic precursors obtained in the following examples were measured for resin filling properties by the following methods.

(1. Resin filling property) Use an optical microscope to observe and take pictures of the surface of the laminated fiber-reinforced plastic precursor with a support at an arbitrary magnification, and calculate the area of the resin filled and unfilled areas, and then use the resin The area ratio of the filling place was evaluated according to the following evaluation criteria. Evaluation A was the most excellent resin filling property, and evaluation D was the lack of resin filling property. It is preferable to evaluate C or higher, and it is more preferable to evaluate B or A. A: The resin filling rate is 95% or more. B: The resin filling rate is 90% or more but less than 95%. C: The resin filling rate is 85% or more but less than 90%. D: The resin filling rate is less than 85%.

[Manufacturing Example 1] Production of resin film 1 (Preparation of thermosetting resin varnish 1) 100 parts by mass of cresol novolac-type epoxy resin "EPICLON (registered trademark) N-660" (manufactured by DIC Corporation), 60 mass Parts of methanol novolac resin "PHENOLITE (registered trademark) KA-1165" (manufactured by DIC Corporation), 15 parts by mass of cyclohexanone and 130 parts by mass of methyl ethyl ketone were added, and they were carefully stirred to dissolve. To this, 180 parts by mass of aluminum hydroxide "CL-303" (manufactured by Sumitomo Chemical Co., Ltd.), 1 part by mass of coupling agent "A-187" (manufactured by Momentive Performance Materials), and 2.5 parts by mass of isocyanate-masked imidazole "G8009L" were added. "(Hardening accelerator, manufactured by Daiichi Kogyo Co., Ltd.), and stirred to dissolve and disperse it to prepare a thermosetting resin varnish 1 having a solid content of 70% by mass. (Production of Resin Film 1) On a 580 mm wide PET film (G-2, manufactured by Teijin DuPont Film Co., Ltd.), the thermosetting resin varnish 1 was applied so as to have a width of 540 mm and a thickness of 15 μm after drying. The thermosetting resin film 1 was produced by applying and drying at 100 ° C for 3 minutes. Using the rheometer "AR-200ex" (manufactured by TA instrument Japan Co., Ltd., φ20mm fixture) and measuring the minimum melt viscosity temperature of the produced resin film 1 at a temperature rise rate of 3 ° C / min, the lowest melt viscosity was obtained. The viscosity temperature is 130 ° C.

[Examples 1 to 7 and Comparative Examples 1 to 6] Production of a fiber-reinforced plastic precursor Then, the resin film 1 produced in Production Example 1 was pressed against an aggregate material, that is, a glass woven fabric (basic weight 12.5 g / m ² , IPC # 1017, substrate width of 550mm, manufactured by Nittobo Industries Co., Ltd.), and using the conditions described in Table 1 or Table 2, it is sandwiched by a heating and pressure roller to press the aggregate and The thermosetting resin is impregnated therein, and thereafter, it is cooled by a cooling roll, and then wound up to produce a fiber-reinforced plastic precursor. The obtained fiber-reinforced plastic precursor was used to evaluate resin filling properties. The results are shown in Tables 1 and 2.

[表 1] Table 1

[表 2] Table 2

As can be seen from Table 1, the fiber-reinforced plastic precursors obtained in the examples are excellent in filling the volume voids of the aggregate, and the resin filling properties can be further improved by combining the conditions. On the other hand, it can be seen from Table 2 that the fiber-reinforced plastic precursor obtained in the comparative example does not have a fiber-reinforced plastic precursor having good resin filling properties. Therefore, according to the manufacturing method of the present invention, a fiber-reinforced plastic precursor having good resin filling properties can be obtained.

1‧‧‧Fiber-reinforced plastic precursor manufacturing device

2‧‧‧ Aggregate delivery device

3‧‧‧Resin film feeding device

4‧‧‧ protective film peeling mechanism

5‧‧‧ protective film winding device

6‧‧‧ Sheet heating and crimping device (film crimping means)

7‧‧‧ sheet pressure cooling device

8‧‧‧ fiber-reinforced plastic precursor winding device

40‧‧‧ Aggregate

40a‧‧‧ Surface of the aggregate (one of the surfaces of the aggregate, one of the two surfaces of the aggregate)

40b‧‧‧ Back side of the aggregate (the other surface of the aggregate, the other side of both surfaces of the aggregate)

50‧‧‧Resin film with protective film

52‧‧‧ protective film

54‧‧‧Resin film (film)

54a‧‧‧ Resin film surface on aggregate side (surface of aggregate side film)

60‧‧‧ Fiber-reinforced plastic precursor

FIG. 1 is a schematic view showing one aspect of a method for producing a fiber-reinforced plastic precursor in the present invention.

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Claims (7)

A method for manufacturing a fiber-reinforced plastic precursor, wherein a fiber-reinforced plastic precursor is manufactured by adhering a thermosetting resin film on one surface of a sheet-like aggregate under an atmospheric pressure. The manufacturing method includes the following steps: : The film and the aggregate are heated and pressure-bonded by a pressure roller having a temperature within a range of + 5 ° C to + 35 ° C, which is the temperature at which the thermosetting resin film exhibits the lowest melt viscosity. The method for manufacturing a fiber-reinforced plastic precursor according to claim 1, wherein a roll line pressure of the pressure roller is 0.2 to 1.0 MPa. The method for manufacturing a fiber-reinforced plastic precursor according to claim 1 or 2, wherein a roller line pressure of the pressure roller is 0.4 to 1.0 MPa. A method for manufacturing a fiber-reinforced plastic includes the steps of hardening a fiber-reinforced plastic precursor obtained by the method for manufacturing a fiber-reinforced plastic precursor according to any one of claims 1 to 3. A method for manufacturing a fiber-reinforced plastic precursor, wherein a fiber-reinforced plastic precursor is manufactured by adhering a thermosetting resin film on one surface of a sheet-like aggregate under an atmospheric pressure. The manufacturing method includes the following steps: : The film and the aggregate are heated and pressure-bonded by a pressure roller and a roll line pressure of 0.4 to 1.0 MPa. The method for producing a fiber-reinforced plastic precursor according to claim 5, wherein the temperature of the pressure roller is lower than the temperature at which the thermosetting resin film exhibits the lowest melt viscosity + 5 ° C. A method for manufacturing a fiber-reinforced plastic includes the steps of hardening a fiber-reinforced plastic precursor obtained by the method for manufacturing a fiber-reinforced plastic precursor according to claim 5 or 6.